CN115697115A

CN115697115A - Article for preventing contamination of contaminant materials

Info

Publication number: CN115697115A
Application number: CN202180026232.2A
Authority: CN
Inventors: 特蕾莎·丹科维奇; 乔纳森·莱维内; 丹尼尔·劳伦斯·纳惠·欧里恩·喀纳斯塔罗-佳尔西亚; 帕特里克·伯恩斯·阿普菲尔德; 瓦特萨尔·嘉普利亚; 罗纳尔德·斯凯耶·兰考讷
Original assignee: Folia Water Inc
Current assignee: Folia Water Inc
Priority date: 2020-04-09
Filing date: 2021-04-09
Publication date: 2023-02-03
Also published as: US20230135711A1; WO2021207663A1; EP4132309A1; CA3179960A1

Abstract

One embodiment is an article configured to inhibit or prevent the growth of a pathogen. The article of manufacture comprises: an inner layer configured to face a wearer's skin when the facial masking article is applied to the wearer's face; an intermediate layer adjacent to the inner layer; and an outer protective layer adjacent to the intermediate layer and opposite the inner layer and comprising a substrate and metal particles in the substrate, wherein the metal particles are configured to inhibit or prevent pathogen growth.

Description

Article for preventing contamination of contaminant materials

Technical Field

The present disclosure relates to articles for inhibiting infection via contaminant materials, and in particular to any cellulosic substrate, textile, polymeric article for inhibiting infection.

Background

Antimicrobial and antiviral products are needed to address the health and safety concerns of people who come into contact with or visit clinical environments such as medical offices, hospitals, and the like. In addition to medical facilities, there is also a need to incorporate antimicrobial and antiviral efficacy into products that are typically in direct contact with the public, including contaminant materials as well as products that may carry infectious microorganisms, such as paper-based products, textiles, nonwovens, and the like. Prevention of pathogen transmission through various surfaces that come into contact with people in everyday use is a significant public health concern.

Current prevention methods employ antimicrobial paper-based filters impregnated with copper particles, as described in U.S. patent No. 9,611,153, and antimicrobial substrates that include silver particles, as described in international patent publication No. WO 2017/124057. However, there is a need for enhanced antiviral and/or antimicrobial paper or textile substrates for use throughout medical facilities including hospital operating rooms and patient care areas, as well as in basic service industries such as grocery stores, garbage collection, and food distribution.

Disclosure of Invention

Embodiments of the present disclosure are a facial masking article. The facial masking article includes an inner layer configured to be placed adjacent to a wearer's skin when the facial masking article is applied to the wearer's face. The inner layer includes thermoplastic fibers and an outer region defining an outer edge of the inner layer. The facial masking article also includes an intermediate layer adjacent to the inner layer. The intermediate layer includes thermoplastic fibers and an outer region defining an outer edge of the intermediate layer. The facial masking article also includes an outer protective layer adjacent the intermediate layer and opposite the inner layer. The outer protective layer has a blend of cellulosic fibers and thermoplastic fibers and metal particles included therein. The metal particles are configured to inhibit or prevent pathogen growth. The layer includes an outer region defining an outer edge of the outer protective layer. At least a portion of the outer region of the inner layer is bonded to the outer region of the outer protective layer. The facial masking article includes an attachment member configured to attach the facial masking article with the wearer.

Embodiments of the present disclosure include a disposable medical article. The disposable medical article further includes at least one substrate layer. The article also includes a protective layer having a substrate and metal particles in the substrate, the metal particles having a size in at least one dimension in a range from 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth.

Another embodiment includes a wound dressing article. The wound dressing article further includes at least one substrate layer. The article also includes a protective layer having a substrate and metal particles in the substrate, the metal particles having a size in at least one dimension in a range from 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth.

Another embodiment includes a packaging article. The packaging article further includes a protective layer having a substrate and metal particles in the substrate, the metal particles having a size in at least one dimension in a range from 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth. Other embodiments of this aspect include corresponding computer systems, apparatus, and computer programs, recorded on one or more computer storage devices, each configured to perform the actions of the methods.

Another embodiment includes an adhesive article. The adhesive article further includes a protective layer having a substrate and metal particles in the substrate, the metal particles having a size in at least one dimension in a range of from 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth. The article further includes an adhesive disposed along one side of the protective layer. The article further includes an optional obscuring layer directly adjacent to and facing the adhesive, the optional obscuring layer configured to be removed to expose the adhesive for placement on a surface.

Drawings

FIG. 1A shows an embodiment of a substrate for use in the articles described herein;

FIG. 1B shows an embodiment of a substrate for use in the articles described herein;

FIG. 1C shows an embodiment of a substrate for use in the articles described herein;

fig. 2A is a front view of a facial masking article according to an embodiment of the present disclosure;

FIG. 2B is a schematic cross-sectional side view of the facial masking article shown in FIG. 2A;

FIG. 3A is a schematic elevational view of the inner layer of the article shown in FIGS. 2A and 2B;

FIG. 3B is a schematic front view of an intermediate layer of the article shown in FIGS. 2A and 2B;

FIG. 3C is a schematic front view of the outer protective layer of the article shown in FIGS. 2A and 2B;

FIG. 4 is a partially assembled exploded view of the article shown in FIGS. 2A and 2B;

FIG. 5 is a detail view of a portion of the facial masking article shown in FIG. 2A;

FIG. 6 is a graph depicting virological test results over time for an outer protective layer sample treated with copper ions;

FIG. 7 is a graph depicting virological test results over time for an outer protective layer sample treated with copper particles;

FIG. 8 is a graph depicting virological test results over time for an outer protective layer sample treated with copper particles;

FIG. 9 is a graph depicting virological test results over time for an outer protective layer sample treated with copper particles;

FIG. 10 is a graph depicting virological test results over time for an outer protective layer sample treated with copper particles; and

fig. 11 is a graph depicting virological test results over time for samples of the outer protective layer treated with silver.

Detailed Description

Embodiments of the present disclosure include articles having metal particles deposited thereon that are suitable for inhibiting or preventing infection from or caused by a contaminated surface or other high contact surface. Referring to fig. 1A-1C, the article 100 described herein may comprise one or more of various types of substrates 104 for various applications. Fig. 1A shows exemplary multi-layer paper-based antimicrobial materials for medical applications, including medical paper towel (tissue), towel (towel), and examination table applications. Fig. 1B shows a 3-layer material consisting of an outer protective layer 102 that includes metal particles, an inner layer that may or may not include metal particles, and an intermediate layer 112 that may include polypropylene. The 3-layer material shown in fig. 1B may be used for disposable garment applications or as a mask article, as further described below. Fig. 1C shows a 2-layer material with a metal nanoparticle protective layer 102 and a base layer 112 for sheeting, table mat, drapes, and other non-apparel uses.

One or more substrates 104 are formed by reducing a metal salt in situ in a continuous process, thereby forming metal particles 108 on the surface of the substrate components. The metal particles 108 may be nano-sized and micro-sized particles. For example, the metal particles 108 may be formed directly on the surface of the fibers forming the substrate 104, as discussed further below. The metal particles 108 may include, for example, silver or copper particles deposited or formed on the article itself. The article 100 described herein can be an antimicrobial paper, an antiviral paper, a textile article, a nonwoven article, or a combination thereof, configured to combat, inhibit, and/or prevent the transmission of pathogenic microorganisms through the surface of contaminants of clothing, furniture, personal Protective Equipment (PPE), packaging, and the like. The article 100 may have antibacterial, antifungal, antiviral, and antiyeast properties.

Typical substrates need to be modified to produce effective infection control articles that limit the persistence of microorganisms on the surface of the contaminant. To produce an antimicrobial material to prevent infection from surfaces in contact with contaminants, the material must absorb a microbially contaminated aerosol and must inactivate the microorganisms within minutes to prevent the transmission of infectious pathogens to others. The use of hydrophilic materials such as paper or cellulose polymer textiles is advantageous because such materials naturally absorb aerosols (water-based droplets containing microorganisms). By adding antimicrobial metal particles, such as nano-silver, nano-and micro-copper particles, to the surface of the fibers, any droplets that come into contact with the surface of the substrate will be quickly absorbed into the fibrous substrate and directly come into contact with the metal particles. Direct contact results in a rapid disinfection process. In some examples, the sterilization process may last for several minutes. To achieve antimicrobial or antiviral elimination in a short desired time, a recommended range for such metal nanoparticle precursors (e.g., silver nitrate or other aqueous silver salts and/or aqueous copper salts) should be between 1ppm and 10,000ppm.

Cellulosic materials that may be used include the following: wood pulp in wet papermaking, air-laid fluff pulp, cotton, viscose, rayon, cellulose blends including materials composed of polypropylene cellulose, polyethylene terephthalate cellulose, and other cellulosic synthetic polymer blends. The particular cellulosic material used depends upon the particular application. The method of adding metal nanoparticles to various cellulose materials depends on the processing of each type of cellulose.

The substrate 104 may be formed from a variety of materials, including fibers. The substrate 104 may include a paper substrate, a paper laminate, a nonwoven laminate, a textile laminate, or a laminate of paper, nonwoven, and/or textile. The substrate 104 may comprise any type of composition, such as cellulose fibers or polymer fibers, as desired. For example, the fibers may include, but are not limited to, natural cellulosic fibers, such as natural wood fibers, natural cotton fibers, synthetic cellulosic fibers, blends thereof, and other hydrophilic fibrous fibers.

The article 100 described herein may be made by methods and materials as described in international patent publication WO2017124057, the entire disclosure of which is incorporated herein by reference. For example, the base substrate may allow the in situ synthesis of metal nanoparticles to be performed on-line on a paper machine or off-line on a coating machine. By extension, the metal ions can be absorbed into the substrate components, such as into the cellulose fibers prior to forming the substrate by a pulp treatment metal ion impregnation process, and reduced to metal nanoparticles during the paper making or coating process.

In order to increase the wettability of hydrophobic fibrous nonwovens (wet-laid or air-laid products), corona discharge treatment ("CDT") may be employed to increase the absorption of the coating liquid. Thus, because of the use of CDT, various nonwovens (plastic and cellulose based) can be coated. Further, for air-laid products, metal particle precursor chemicals may be added to the fibers along with a binder (e.g., along with a latex binder typical in air-laid processes) in order to create the metal particles 108 in the substrate 104. Such binders are typically added to the fiber network in the form of a spray or foam in an air-laid process and then activated by heat from a dryer to cure the binder. Because thermal energy also catalyzes metal particle synthesis in a continuous process, a spray or foam application of a mixture of binder, metal salt, and other reducing agent can be added to the substrate. This can lead to the formation of metal nanoparticles in the airlaid papermaking process. This result can provide an antimicrobial and/or antiviral article.

Continuous processes as described herein have a number of advantages over batch processes. For example, the continuous process described herein allows for the production of large quantities of nanoparticle-embedded paper within minutes, as opposed to a batch process. Continuous processes as described herein may utilize, for example, dixon coaters, fourdrinier pilot machines, and other commercial large-scale papermaking production lines. For example, a relatively small Dixon coater is coated and dried on a 12 inch roll of paper running at full speed of 280 linear feet per minute (ft/min). The speeds that Fourdrinier pilot plant can produce typically range from 10 feet per minute to 300 feet per minute, far exceeding the level of production possible in the previously disclosed invention (Dankovich, 2015). Larger commercial papermaking lines are capable of higher throughputs, typically 500 feet/minute to 2500 feet/minute. The previously disclosed conventional batch processes for nanoparticle synthesis have not been adapted to this powerful technique and, therefore, they have not been widely adopted.

The present disclosure includes the continuous production of large quantities of metal nanoparticles directly on a substrate, rather than synthesizing the metal nanoparticles in a separate filter sheet in a batch process as previously described (Dankovich, 2014). Thus, embodiments described herein include methods for synthesizing metal nanoparticles within a substrate within seconds rather than minutes or hours as compared to batch processes. The result is a significant increase in the production rate of the cellulose material producing the embedding of the metal nanoparticles therein. Furthermore, the inventive concepts described herein do not significantly alter the surface chemistry of the pulp or paper during wet forming of the substrate. Furthermore, the methods described herein do not significantly alter the physical properties of the resulting substrate as compared to the same method without the nanoparticle synthesis step. The in situ method of forming nanoparticles directly on the surface of the fiber has other advantages over previous batch processes. For example, by using an in situ synthesis method as described herein, the level of total metal nanoparticles formed and retained in the substrate is at least much higher than the absorption method of nanoparticles (Dankovich and Gray, 2011). The in situ synthesis methods as described herein can prevent excessive loss of expensive metal reagents during the manufacturing process and product use stage. There may be little to no loss of metal precursor during this manufacturing process due to the recycling of the solution in the application unit.

In the illustrated embodiment (fig. 2A-5), the present disclosure includes a facemask application of a substrate 104 having metal particles 108, wherein the metal particles 108 are bonded to their fibers. 104 and 204 may be used interchangeably in this disclosure to identify a substrate or substrate layer; and 108 and 208 may be used interchangeably to identify metal particles.

Referring to fig. 2A and 2B, article 100 is an antiviral and antimicrobial facial mask article configured to mask the nose and mouth of a user. The facial masking article 100 may be a medical or surgical mask. In the embodiment shown, the face screening article is a three-layer material, although more than three layers of material may be used.

As shown in fig. 2A-4, the facial masking article 100 includes an inner layer 203, an intermediate layer 205, and an outer protective layer 206 adjacent to the intermediate layer 205. The inner layer 203 is configured to face the user's skin when the facial masking article 100 is applied to the user's face. The outer protective layer 206 is opposite the inner layer 203 and is configured to face away from the wearer's skin when the facial masking article 100 is applied to a user's face. 203. 205 and 206 each further includes outer regions 210a, 201b, 210C (fig. 3A-3C) defining an outer edge 211 of the article 100. The outer edge 211 extends around the nose and mouth of the user when the user is wearing the facial mask article 100. In the embodiment shown, the inner layer 203, the intermediate layer 205, and the outer protective layer 206 are configured to be bonded together, as explained further below.

The facial masking article 100 has two states, undeployed and deployed. In an undeployed state, the facial mask article 100 has a length extending in the longitudinal direction 2L and a width W extending in a vertical direction 4 opposite to the longitudinal direction 2 ₁ . In the embodiment shown, the length L may be about 175.0cm, and the width W ₁ May be about 95.0mm. In alternative embodiments, the dimensions of the facial masking article 100 may vary.

The article 100 has an upper portion 207 and a lower portion 209 opposite the upper portion 207 in the vertical direction 4. In addition, the article 100 has a face portion 212 and a back portion 216 opposite the face portion 212 in a lateral direction 6 perpendicular to the longitudinal direction 2 and the vertical direction 4. When the facial mask article is applied to a user's face, the face 212 is configured to be exposed to the user's surroundings and the back 216 is configured to face the user's skin. The facial masking article 100 includes one or more pleats 218, which pleats 218 extend along a length L on the face 212 of the article 100. Pleats 218 are configured to expand facial shield article 100 when article 100 is applied to a user's face and worn. Pleats 218 are also configured to enable article 100 to be divided into three folds.

The article 100 also includes a nose strip or bridge strip 221. Nose piece 221 is configured to conform the fit of article 100 to the nose of a user when article 100 is applied to the user's face and worn. The nose piece 221 may be made of aluminum or bendable plastic. The nose piece 221 may be positioned on the upper portion 207 of the article and may be welded in place. In the illustrated embodiment, the length L of the nose piece _N May be about 100.0mm, have a width of about 3.0mm and a thickness in the range of about 0.3 to 0.8mm. In alternative embodiments, the nose piece may vary.

Referring to fig. 3A-4, inner layer 203 includes an upper surface 220 and a lower surface 224 opposite the upper surface. When the facial masking article 100 is applied to a user's face, the lower surface 224 is adjacent to the user's skin.

Inner layer 203 includes one or more pleats 218 _S Said pleats 218 _S Extending parallel to each other along the length L of the inner layer 203. The one or more pleats 218 _S Is configured to deform the inner layer 203 between an expanded state and an unexpanded state when the facial masking article 100 is applied to a user's face and worn. In the deployed state, the length L of the inner layer 203 is about 175.0mm, and the thickness isThe degree T is about 0.16mm. The width WP of the inner layer 203 is about 195.0mm. In alternative embodiments, the length L, thickness T, and width WP of inner layer 203 can vary.

The inner layer 203 may be formed from a nonwoven laminate material. For example, the inner layer 203 may be a spunbond substrate, a meltblown substrate, or a laminate of a spunbond substrate and a meltblown substrate. In such embodiments, the inner layer 203 may be a laminate of SMS, SMMS, or the like. In the embodiment shown, the inner layer 203 is formed from a polypropylene (PP) laminate as described above. Further, the inner layer 203 has a basis weight ranging from 20.0gsm (grams per square meter) to about 80.0gsm.

Middle layer 205 includes one or more pleats 218 _M Said pleats 218 _M Extending parallel to each other along the length L of the intermediate layer 205. The one or more pleats 218 _M For deforming intermediate layer 205 between an expanded state and an unexpanded state when facial masking article 100 is applied to a user's face and worn. In the expanded state, the intermediate layer 205 has a length L of about 175.0mm and a thickness T of about 0.16mm. Width W of intermediate layer 205 _M Narrower than the width WP of the inner layer 203. In the embodiment shown, the width W _M Is about 175.0mm. In alternative embodiments, the length L, thickness T, and width W of the intermediate layer 205 _M May vary.

The intermediate layer 205 includes a front surface 225 and a back surface 226 opposite the front surface 225. The back surface 226 is adjacent to the upper surface 220 of the inner layer 203 such that the middle layer 205 is on top of the inner layer 203 and is the same size as the inner layer 203. The middle layer 205 may be formed from a nonwoven laminate material. For example, the intermediate layer 205 may be a spunbond substrate, a meltblown substrate, or a laminate of a spunbond substrate and a meltblown substrate. In this embodiment, the intermediate layer 205 may be a stack of layers of SMS, SMMS, or the like. In one example, the intermediate layer is a meltblown electrostatically charged substrate. In the embodiment shown, the intermediate layer 205 is formed from a polypropylene (PP) laminate as described above.

The outer protective layer 206 is configured to face outwardly away from the wearer's face when worn. Further, the outer protective layer 206 is configured to inhibit or prevent antimicrobial growth and viral transmission. As shown, the outer protective layer includes a top surface 228 and a bottom surface 232 opposite the top surface 228. The bottom surface 232 is adjacent the front surface 225 of the middle layer 205 such that the outer protective layer 206 is on top of the middle layer 2045 and is the same size as the middle layer 205 and the inner layer 203.

Outer protective layer 206 also includes one or more pleats 218 _P Said pleats 218 _P Extending parallel to each other along the length L of the outer protective layer 206. The one or more pleats 218 _P Is configured to deform the outer protective layer 206 between an unexpanded state and an expanded state when the facial masking article 100 is applied to a user's face and worn. In the unfolded state, the outer protective layer 206 has a length L of about 175.0mm and a thickness T of about 0.16mm. The width WS of the outer protective layer 206 is narrower than the width WP of the inner layer 203 but is wider than the width W of the intermediate layer 205 _M And (4) wide. In the embodiment shown, the width WS is about 183.0mm. In alternative embodiments, the length L, thickness T, and width WS of the outer protective layer 206 may vary.

The outer protective layer 206 is composed of a substrate containing metal particles formed at least on the surface thereof. In the example shown, the outer protective layer is a nonwoven material comprising a blend of short cellulose fibers and short thermoplastic fibers. In one particular example, the outer protective layer is a nonwoven material that includes a blend of short cellulose fibers and short polypropylene fibers (e.g., PP fibers). The outer protective layer 206 may have 50 to 90 weight percent cellulosic fibers and about 10 to 50 weight percent thermoplastic fibers. The outer protective layer 206 has a basis weight of about 16.0gsm to about 45.0gsm. In one example, the outer protective layer has a basis weight of at least 16.0gsm. In another example, the outer protective layer has a basis weight of up to about 45.0gsm. In another example, the outer protective layer has a basis weight of about 20.0gsm to 40.0gsm. In another example, the outer protective layer 206 has a basis weight of about 24.0gsm.

The outer protective layer 206 may include a plurality of metal particles 208. The metal particles 208 are configured to inhibit or prevent pathogen growth. The metal particles 208 range in size from 1 nanometer to about 200 nanometers in at least one dimension. In the embodiment shown, the metal particles 208 include at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof. In one embodiment, the metal particles are formed in situ during processing of the substrate to form 0.05gsm to about 1.5gsm of metal particles on the outer protective layer 206. In one example, the outer protective layer 206 includes at least 0.05gsm of metal particles. In another example, the outer protective layer 206 includes up to about 1.5gsm of metal particles. In another example, the outer protective layer 206 includes about 0.6gsm of metal particles. In another example, the silver content of the outer protective layer 206 may be 0.5 wt% to 5.0 wt% per gram of the outer protective layer 206 substrate. In another example, the silver loading in the outer protective layer 206 may be about 2.2 wt% per gram of the outer protective layer 206 substrate. The metal particles range in size in at least one dimension from 1 to about 200 nanometers. As further explained, the result was a facial mask article with an antiviral log reduction of at least 4.0, an average filtration efficiency of at least 99.71%, and a bacterial filtration efficiency of at least 99.37%.

In one embodiment, the outer protective layer 206 may be made of 99.9% pure silver. In one example, the outer protective layer 206 includes an antimicrobial silver preservative coating that releases silver into microbe-laden water droplets on the protective layer 206. The silver content of the outer protective layer 206 may be 0.2 wt% to 1.0 wt% per gram of the outer protective layer 206 substrate. In another example, the silver loading in the outer protective layer 206 may be about 0.5 wt% per gram of the outer protective layer 206 substrate. This configuration inhibits microbial colonization on the outer protective layer 206 and the article 100. The outer protective layer 206 may be subjected to ultraviolet treatment. Uv treatment may be used to drive completion of silver fixation. This configuration may enhance the resistance of the outer protective layer 206 to environmental factors such as aging or silver release. In one example, the outer protective layer 206 may be subjected to ultraviolet treatment and high ultraviolet exposure such that 1) the fixation rate of silver on the substrate is greater than 90%, and 2) the outer protective layer 206 exhibits greater resistance to aging (i.e., no change in appearance or darkening of the outer protective layer 206).

The outer protective layer 206 is made of a blend suitable for ultrasonic welding with the intermediate layer 205 and the inner layer 203. This configuration enhances the breathability and pressure drop properties of article 100. As shown, the inner layer 203, the intermediate layer 205, and the outer protective layer 206 are bonded together at their respective outer regions by ultrasonic welding. However, in another embodiment, the inner layer 203, the intermediate layer 205, and the outer protective layer 206 may be bonded together by other thermal or chemical means (e.g., heat or embossing). In alternative embodiments, the inner layer 203, the intermediate layer 205, and the outer protective layer 206 may also be joined together by other attachment means.

In this configuration, the outer protective layer 206, and thus the facial masking article 100, may be antimicrobial and/or antiviral through the addition of metal particles such as silver or copper. In another embodiment, the metal cellulose component may be disposed just inside the outer protective layer 206 to form a 4-layer face-covering article. In an alternative embodiment, a metal cellulose material may be added as a protective patch on top of the outer protective layer 206.

Referring to fig. 5, facial masking article 100 also includes an attachment member 240, which attachment member 240 is configured to attach facial masking article 100 to a user. In the embodiment shown, the attachment member 240 includes one or more straps 242, the one or more straps 242 being coupled with the upper portion 207 and the lower portion 209 of the facial masking article 100. In the embodiment shown, the attachment member 240 includes a first strap 242A coupled to the upper portion 207 and the lower portion 209 at one end of the face screening article 100 and a second strap 242B coupled to the upper portion 207 and the lower portion 209 at the opposite end of the face screening article 100. The first strip 242A and the second strip 242B may be coupled at the outer edges 211 of both the inner layer 203 and the outer protective layer 206. In the embodiment shown, the first strip 242A and the second strip 242B are elastic strips having a length of about 175.0mm and a width of about 3.0mm. The

strips

242A, 242B are coupled to the outer edge 211 by a weld. In this configuration, the

straps

242A, 242B may be telescopic and may be easily adapted to the user's facial proportions. In alternative embodiments, other materials and attachment means may be employed in the attachment member 240.

Examples

Example 1: preparation and Performance testing of Metal particles added to protective layer

In this example, virological tests were performed on samples of paper material impregnated with silver and/or copper species to test the samples for antiviral efficacy. The model systems used were phages (as viral representatives) and E.coli (Escherichia coli, as host representatives). Plaque assay was used as an efficacy measurement. Plaque assay is used for virus isolation/purification and to determine virus titer. Viral titer, also known as viral load or burden, is a numerical expression that quantifies the amount of virus in a given volume of fluid. Plaque assay is an optimized virological method for counting and measuring the infectivity of phages.

Materials and methods

Seventeen (17) parts of base paper were provided as samples. Samples 1-4, 9-13, and 16-17 are polypropylene cellulose blends. These base papers contain about 25-35% polypropylene and about 65% -75% cellulose. Samples 5-8 and 14-15 are 100% pure cellulose blends. Impregnating some of the base paper with silver or copper species; the other base papers were not impregnated. The identity of each sheet is blind to the primary investigator, i.e., the sheets are marked with numbers between 1 and 17, with no other distinguishing mark. Each sheet was cut and loaded into a 24-well plate. The efficacy of the test was repeated three (3) times at 4 different incubation time points (i.e. 5 minutes, 30 minutes, 1 hour and 4 hours) for each cut paper. The experimental set-up is shown on the right. The efficacy of paper surfaces to mitigate viral transmission and replication was studied using the method reported by Doremalen et al (2020).

Phage was used in this comparative study to demonstrate protocol validation. P1 bacteriophage, a temperate bacteriophage that infects escherichia coli (e. Coli) and some other bacteria, is used as a representative of the virus.

The experimental design is divided into seven (7) independent but interrelated tasks:

1. paper material preparation

2. Phage reproduction

3. Harvesting of viruses

4. Agar plate preparation

5. Bacterial culture

6. Bacterial cell culture exposed to viral harvest

7. Phage titer determination

A known amount of virus titer stock solution was deposited on the surface of each cut paper material. After incubation for 5 minutes at room temperature (21-23 ℃) and 40% relative humidity, the first set of materials was analyzed for virus replication. One (1) ml of the collection medium was used to recover the virus. The virus titer harvest medium was added to the E.coli culture, placed in an incubator at 37 ℃ for 24 hours, and then quantified by counting Plaque Forming Units (PFU). Titers of virus stock solutions were calculated as PFU per milliliter (mL) (Dulbecco & vogt.1953).

After plaque counting for each dish, the values were recorded and plotted as PFU as a function of culture time. The log reduction was calculated using plates of 5-100 plaques using the following formula:

wherein the initial viral load of the group A and B papers is 1.45x10 ⁶ PFU/mL, 1.75x10 for group C paper ⁷ PFU/mL. The end viral load is the value of PFU assessed after each incubation period (e.g., 100 counted plaques equates to 100 PFU/mL). Each log reduction value is contained in the table of the results portion immediately to the right of each plaque count. The starting viral load was calculated as the average PFU/mL from the titer curve (Sanders 2012 and Andersson and Lood2019; bear 2014.

Results

The results of this assay indicate that the silver or copper loaded paper exhibits antiviral properties relative to the control paper (i.e., paper not loaded with silver or copper species). The papers that exhibited the highest amount of antiviral efficacy are sample numbers 12 and 16. The numerical values of the log reduction values for each sample are contained in tables 1 and 2 below.

TABLE 1

Table 2:

the following tabulated data includes paper sample numbers 12, 13, 14, 15, 16 and 17.

Table 3:

the results of the time-dependent average plaque forming units studies for samples 12-17 are shown in FIGS. 6-11, respectively.

The paper materials in group A (maroon; 13, 14, 15, 16 and 17) were coated with a copper species and performed very well in the antiviral efficacy test. The results of the plaque assay showed that the mean PFU counts had a smaller standard deviation in the replicates. Preliminary evidence indicates that sample No. 16 (Ahlstrom-coffee filter paper-copper particles) performed best compared to all papers in the group, i.e., the paper effectively reduced plaque formation at the highest log reduction value for the lowest incubation period.

The paper materials in group B (white; 1, 5, 7, 9 and 11) perform poorly in the antiviral test. Preliminary results indicate that no antiviral efficacy was found in all papers tested.

The paper materials in group C (brown; 2, 3, 4, 6, 8, 10 and 12) were coated with silver species, most of which performed well in the antiviral efficacy test. As with the results of group a, the results of the plaque assay showed that the mean PFU counts had a smaller standard deviation in the replicates. Preliminary evidence indicates that sample No. 12 (Ahlstrom-mask P-P blend-silver low-medium) performed best compared to all papers in the group, i.e., the paper was effective at reducing plaque formation with the highest log reduction value.

Example 2: efficiency of particle filtration

In this example, a procedure was performed to evaluate the inactive Particle Filtration Efficiency (PFE) of the test articles.

Materials and methods

Monodisperse polystyrene latex spheres (PSL) were sprayed (misted), dried and passed the test article. Particles that passed the test article were counted using a laser particle counter.

With test articles in the system, a one minute count is performed. Control counts of one minute were made without test articles in the system before and after each test article count. Control counts were performed to determine the average particle number delivered to the test article. The number of particles that permeated through the test article was used to calculate the filtration efficiency as compared to the average control value. During the test and control periods, the air flow rate was maintained at 1 cubic foot per minute (CFM) ± 5%.

The procedure used the basic particle filtration method described in ASTM F2299 with some exceptions; notably, this procedure involves a non-neutral challenge. In actual use, the particles carry a charge, and thus this challenge represents a more natural state. Non-neutral aerosols are also specified in FDA guidelines for surgical masks. And the acceptance standard of all test methods is met. Testing was performed according to the U.S. food and drug administration Good Manufacturing Practice (GMP) regulation 21c.f.r.

parts

210, 211 and 820.

Test article: 102420A-7 samples; 102420B-7 samples; 102420E-7 samples

And (3) testing side: inner part

Area of test: 91.5cm ²

Granularity: 0.1 μm

Laboratory conditions: 3, month 16 in 2021: at 2204, 21.2 ℃ and Relative Humidity (RH) 22%;2252 at 21.1 deg.C and RH 22%;2308 at 20.9 deg.C and RH 22%; 21/3/2021: 21.2 ℃ at 1401, RH 22%;1446 at 21.0 deg.C and RH 22%.

Results

The results of the study are shown in tables 4-6 below.

TABLE 4

The average filtration efficiency of the test article was 99.71% with a standard deviation of 0.024.

Table 5:

the average filtration efficiency of the test article was 99.67% with a standard deviation of 0.071.

Table 6:

the average filtration efficiency of the test article was 99.66% with a standard deviation of 0.100.

Example 3: bacterial filtration efficiency

In this example, a procedure was performed to evaluate Bacterial Filtration Efficiency (BFE) of the test products.

Materials and methods

Five samples were used to test the articles. The samples were treated for 4 hours at 20.4-22.1 ℃ and 83-86% RH. The test setup involved the following:

area of test sample (cm) ² )	48.3
		Challenging sample side	Interior of the mask
Flow rate (LPM)	28.3
		Average + control plate count	2542
Average particle diameter (μm)	3

Results

The results of the bacterial filtration efficiency test are reported below:

table 7:

example 4: cleanliness of microorganisms

In this example, the test articles were tested for microbial cleanliness (bioburden) of the test articles.

Materials and methods

The articles were tested using a minimum of 5 samples. The test was performed using the Standard Test Protocol (STP) numbered STP 0036 (version 15). The tests were carried out according to EN 14683, 2019 and ANSI/AAMI/ISO 11737-1. The counts measured on the product are colony forming units and may not reflect individual microorganisms. Testing was performed according to the U.S. food and drug administration Good Manufacturing Practice (GMP) regulation 21c.f.r.

parts

210, 211 and 820.

The program includes the following:

results

The results were recorded as Colony Forming Units (CFU) for each test article. "UTD" occurs because the count at the first flush is zero.

Table 8:

<= no organism tested

UTD = not determined

Example 5: summary of various test results

In this example, the test articles were tested for bacterial filtration efficiency, particulate filtration efficiency, viral filtration efficiency, microbial cleanliness (bioburden), synthetic blood permeation resistance, and apparel textile flammability. The results are summarized in the table below. Results for bacterial filtration efficiency, particulate filtration efficiency, bioburden, synthetic blood permeation resistance, and apparel textile flammability also apply to test articles having antimicrobial silver preservative coatings as described above.

Table 9:

the criteria in the table include the version that was in effect at the time of filing the application.

Example 6: coating test

In this example, a coating test was performed on the substrate layer of the test article. Each test subjects the substrate layer of the test article to a different coating. The results are recorded, including a comprehensive information of the challenges and potential failure modes encountered.

Test A

In this test, a batch of underlay paper samples were coated with a silver load of 0.5gsm and a coat weight of 11.26 gsm. A second sample of backing layer paper was coated with a silver loading of 1.04gsm and a coat weight of 10.85 gsm. The range of 250-300F for the dry portion was determined as the limit to achieve the desired silver loading on the paper. The change in the angle of the slot die was observed to improve the spreading of the solution on the paper. The effects of gravity and slot angle can cause a pressure differential across the edge of the paper.

Test B

In this test, a sample of backing paper was coated with a coating weight of 17.6gsm and a silver weight of 0.52 gsm. A 30% solids solution was observed to be coated. Single and double side coating was verified using a high viscosity 30% solids solution (0.5% guar). The coating weight and silver loading was observed to increase by a factor of 2 from single-coated paper to double-coated paper. The% silver fixation did not increase to the same extent. The finished roll was observed for discoloration by ultraviolet light exposure. An increase in% silver fixation from 22% to 33% was observed compared to the discolored and non-discolored areas.

Test C

In this test, the backing paper sample was coated with a coat weight of 13.304gsm and a silver loading of 0.675 gsm. Successful method validation of the coating was observed using a 40% solids solution (1. The use of guar was observed to control coating weight by reducing the saturation of the paper, by increasing soak/wicking time, compared to non-guar coating solutions. Changes in the added guar concentration were observed from a coat weight reduction of 25.0gsm to an average of 13.0gsm (e.g., 0.35% and 0.3% for a desired viscosity of 500 cPs). The coating line speed can be increased from 15fpm to 35fpm with similar appearance but different coating aesthetics. Higher web speeds (web speed) were observed to deposit less volume of solution, with shorter "residence time" in the dryer, resulting in lower silver loading and lower% silver fixation.

Test D

In this test, the backing paper sample was subjected to an ultraviolet curing step. Heating the solution from 15 ℃ to 30 ℃ resulted in the observed high shear, increased solubility of the chemicals. Complete mixing of the coating solution was observed to be difficult due to the high solids content (40%). It was also observed that the variations in engraving of the gravure printing cells resulted in an increase or decrease in the coating weight/add-on. The dryer temperature increases. It was also observed that higher dryer temperatures resulted in increased silver reduction and higher silver fixation. For example, increasing the dryer temperature from 250 ° F to 275 ° F increases the silver fixation from 54% to 74%.

The coated roller was treated with uv treatment. It was observed that uv curing using 40 inch uv curing line pushed the silver fixation to completion (thereby enhancing the sample's resistance to environmental factors such as aging or silver release). For example, the silver retention was observed to increase to greater than 90% for all paper samples. No extreme changes in material or surface properties were observed; however, the width of the paper sample was reduced by 1%. A color gradient was observed due to the uneven uv exposure caused by the unbalanced direction of the uv bulb. It was also observed that optimization of cure line process parameters can ensure reliable and repeatable finished products for future testing.

Aging studies were performed on the uv materials. The uv cured samples were subjected to accelerated aging with a color gradient (i.e., non-uniform intensity). It was observed that the areas with high uv exposure showed greater resistance to aging (i.e. no change in appearance/darkening). It was observed that the areas less exposed to uv light were susceptible to moisture and heat, resulting in non-uniform discoloration of the coated paper samples.

Additional embodiments include a variety of medical and consumer applications having a substrate with metal particles bonded to its fibers, including but not limited to 1) respirators (e.g., N95 respirators); 2) Inspecting table products; 3) Disposable articles such as gowns (gown), drapes (drapee), cloaks, privacy curtains, doors and dental bibs; 4) Disposable bedding articles and related articles; 5) A wound dressing; 6) High contact products such as secondary packaging including paper grocery and delivery bags, paper and paperboard packaging, mail envelopes, mailers, and the like; and 7) adhesive-backed articles or papers configured to adhere to a surface (e.g., decals, etc.)

In one embodiment, the article 100 may be a filtering face mask N95 respirator (FFM). The metal cellulose material is integrated into the FFM. The FFM may be composed of multiple layers of nonwoven material and may have metal cellulose material added in a manner similar to the facial mask articles described above.

In one embodiment, article 100 is a disposable product for use on medical examination tables. Disposable products for inspection tables are typically 2-ply or 3-ply paper towels (tissue paper) that are cut to 40 inches by 48 inches or other sizes for use in medical inspection table paper, or sold in roll form for mounting on a table. The basis weight of the medical table paper may be between 50gsm and 75gsm depending on the number of layers held together by thermal or chemical means. The texture of medical table paper can be smooth, corrugated, or air-laid, and can be made from virgin or recycled wood pulp or fluff pulp. During paper formation, the metal particles may be embedded or deposited on the cellulose or absorbent material. Thus, the inspection paper itself may have metal particles or inhibit or prevent pathogen progression.

In one embodiment, the article is a disposable medical article. A disposable medical article as described herein can include a multilayer substrate consisting of a tissue, a spunbond polypropylene film, and a paper towel. The polymeric barrier disposed along the interior of the product may prevent fluid from penetrating the skin of the user. To add metal nanoparticles to such materials, the tissue plies may need to be treated on or off the paper machine according to the method described in PCT publication No. WO 2017124057. During the conversion process, a polymeric barrier layer is added by a lamination process. At least one of the two towel layers may have added metallic silver particles or added metallic copper particles. The tissue may be from 20gsm to 25gsm and may be made from recycled or virgin wood pulp. The tissue texture may be creped, smooth, or air-laid. After the three-ply material is assembled, the material can then be embossed, cut to size, and adhered or otherwise attached to form disposable antimicrobial medical garments, such as patient capes, gowns and gowns, and frosted shirts and pants.

In one embodiment, the article 100 may be a disposable bedding article. Disposable bedding articles may include antiviral sheets, antimicrobial sheets, blankets, pillow cases, drapes, and other non-apparel uses. These products have different product specifications than medical apparel. The sheet product may be a fitted sheet or a flat sheet. The fitted sheet includes a resilient border to help secure the sheet to the mattress. Disposable sheets need to be more durable than garments and are therefore typically made from a blend of rayon, cotton, airlaid cellulose and polyester textile materials. To add antimicrobial and/or antiviral particles to these bed sheets, the rayon fibers and/or yarns may be subjected to a coating process to add metal ion precursors and follow the synthetic method described in PCT publication No. WO 2017124057. After the synthesis of the metal nanoparticles on the rayon fibers, the nano-metal rayon fibers can be mixed with polyester fibers into a knitted or woven textile. Bedding articles, such as bedsheets, may have a polypropylene substrate as an impermeable layer to prevent diffusion of liquids that may contain infectious agents in a medical environment. The top layer with the antimicrobial and/or antiviral tissue will still provide absorbency and help keep infectious agents in contact with the metal particle biocide.

In one embodiment, article 100 may be a wound care product. Wound care products may include bandages, wound dressings, and the like. The wound care product may comprise at least one substrate layer comprising metal nanoparticles. The wound care product may also include a protective layer having a substrate and metal particles in the substrate. The metal nanoparticles range in size in at least one dimension from 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth. The metal particles include at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof. The protective layer may be paper, a woven material, a nonwoven material, or a laminate thereof. The protective layer is antimicrobial and antiviral. One or both of the substrate layer and the protective layer may be absorbent. The substrate layer may be formed according to the processes and methods described in PCT publication WO 2017124057.

In one embodiment, the article 100 may be a high contact product or package. High contact products can be formed, such as secondary packaging, including paper grocery bags, paper and paperboard packaging. If various surfaces are exposed to infectious agents, contaminated surfaces may form on various types of packaging, grocery bags, envelopes, and cartons. Such infectious agents may be reduced or eliminated if the surface of the package is embedded with silver particles (e.g., nano-silver), copper particles (e.g., nano-copper). The method is applicable to a large quantity of cellulosic material to produce all types of secondary packaging including kraft pulp, recycled (recycled) pulp and paper, molded fiber (pulp), mechanical pulp, sulfite pulp, and the like. In addition, the metal precursor can be added as a surface coating to the base paper by a surface coating process, such as grocery sack paper, office paper, corrugated board, other cardstock, mail envelopes, mail packaging, and the like.

The article may include a protective layer having a substrate and metal particles in the substrate, the metal particles having a size in at least one dimension in a range from 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth. The metal particles may include at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof. The metal particles may also comprise silver or copper. The protective layer may be paper, a woven material, a nonwoven material, or a laminate thereof. The protective layer may be antimicrobial and antiviral. The packaged article may be a mail envelope, bag, envelope, or carton.

In one embodiment, the article 100 may be adhesive. The adhesive article may include 1) a cellulosic substrate having embedded therein a component, such as fibers, of metal particles or a cellulosic substrate, and 2) an adhesive layer that aids in adhering the article to a surface. Likewise, the cellulosic substrate may be formed according to the methods described in PCT publication WO2017124057, the entire disclosure of which is incorporated by reference into the present disclosure. A masking layer may be applied to protect the adhesive until use. During use, the masking layer is removed and the article is placed on its intended surface. The adhesive adheres the substrate to the desired surface.

The adhesive article may include a protective layer having a substrate and metal particles in the substrate, the metal particles having a size in at least one dimension in a range from 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth. The adhesive article may further include an adhesive disposed along one side of the protective layer. The adhesive article may further include an optional masking layer directly adjacent to and facing the adhesive, the optional masking layer configured to be removed to expose the adhesive for placement on a surface. The metal particles may include at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof. The metal particles may comprise silver or copper. The protective layer may be paper, a woven material, a nonwoven material or a laminate thereof. The protective layer may be antimicrobial and antiviral.

Any suitable method may be used to make the articles described herein. In several cases, the metal particles are added at the substrate manufacturing stage, for example during paper forming, or by roller coating, both of which are described in PCT publication WO 2017124057. However, the articles described herein may be manufactured using any particular means to apply the metal nanoparticles thereof, including by a spraying mechanism or other means. In other words, as described herein, the infection-inhibiting component, e.g., silver or copper, may be applied at any stage of the article's manufacture.

While the disclosure has been described with respect to a limited number of embodiments, these specific embodiments are not intended to limit the scope of the disclosure, which is otherwise described and claimed herein. The precise arrangement of the various elements and the order of the steps of the articles and methods described herein are not limiting. For example, although the steps of the methods are described with reference to the sequence of reference symbols in the block diagram progression, the methods may be performed in the order as desired.

Claims

1. A facial masking article comprising:

an inner layer configured to be placed adjacent to a wearer's skin when the facial masking article is applied to the wearer's face, the inner layer comprising thermoplastic fibers and an outer region defining an outer edge of the inner layer;

an intermediate layer adjacent to the inner layer, the intermediate layer comprising thermoplastic fibers and an outer region defining an outer edge of the intermediate layer;

an outer protective layer adjacent to the intermediate layer and opposite the inner layer, the outer protective layer having a blend of cellulosic fibers and thermoplastic fibers, and metal particles included therein, the metal particles configured to inhibit or prevent pathogen growth, and an outer region defining an outer edge of the outer protective layer, wherein at least a portion of the outer region of the inner layer is bonded to the outer region of the outer protective layer; and

an attachment member configured to attach the facial masking article with the wearer.

2. The facial masking article of claim 1, wherein the metal particles range in size in at least one dimension from 1 to about 200 nanometers.

3. The facial masking article of claim 1 or claim 2, wherein the metal particles are formed at least on an outer surface of the outer protective layer.

4. The facial masking article of any one of claims 1 to 3, wherein the outer protective layer comprises from 0.05gsm to about 1.5gsm of metal particles.

5. The facial masking article of any one of claims 1-3, wherein the outer protective layer comprises up to about 1.5gsm of metal particles.

6. The facial masking article of any one of claims 1-3, wherein the outer protective layer comprises at least about 0.6gsm of metal particles.

7. The facial masking article of any one of claims 1-6, wherein the metal particles comprise at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof.

8. The facial masking article of any one of claims 1 to 6, wherein the metal particles comprise silver.

9. The facial masking article of claim 8, wherein the outer protective layer comprises from 0.05gsm to about 1.5gsm of silver particles.

10. The facial masking article of claim 8, wherein the silver content of the outer protective layer per gram of outer protective layer is from 0.5 wt% to 5.0 wt%.

11. The facial masking article of any one of claims 1 to 7, wherein the metal particles comprise copper.

12. The facial masking article of any one of claims 1 to 11, wherein the outer protective layer is a nonwoven material comprising short cellulosic fibers and thermoplastic fibers.

13. The facial masking article of any one of claims 1 to 12, wherein the outer protective layer is antimicrobial.

14. The facial masking article of any one of claims 1 to 13, wherein the outer protective layer is antiviral.

15. The facial masking article of any one of claims 1 to 13, wherein the inner layer, the intermediate layer, and the outer protective layer are ultrasonically welded together at their respective outer regions.

16. The facial masking article of any one of claims 1 to 13, wherein one or more of the inner layer, the intermediate layer, and the outer protective layer has one or more pleats.

17. A facial masking article according to any one of claims 1 to 13, wherein the attachment member is one or more elastic bands or non-woven bands.

18. The facial masking article of any one of claims 1 to 13, wherein the basis weight of the outer protective layer is from about 16.0gsm to about 45.0gsm.

19. The facial masking article of any one of claims 1 to 13, wherein the outer protective layer has a log antiviral reduction of at least 2.0.

20. The facial masking article of any one of claims 1-13, wherein the facial masking article has an average filtration efficiency of at least 99.71%.

21. The facial masking article of any one of claims 1 to 13, wherein the facial masking article has a bacterial filtration efficiency of at least 99.37%.

22. The facial masking article of any one of claims 1 to 13, wherein the outer protective layer has a basis weight of from about 16.0gsm to about 45.0gsm, metal particles ranging in size from 1 to about 200 nanometers in at least one dimension from 0.05gsm to about 1.5gsm, an antiviral log reduction of at least 2.0, an average filtration efficiency of at least 99.71%, and a bacterial filtration efficiency of at least 99.37%.

23. A facial masking article according to claim 22, wherein the outer protective layer is a nonwoven material comprising short cellulosic fibers and short thermoplastic fibers,

wherein the inner layer and the intermediate layer are nonwoven substrates comprising thermoplastic fibers,

wherein the basis weight of the inner layer is from about 20.0gsm to about 80.0gsm,

wherein the intermediate layer has a basis weight of from about 20.0gsm to about 80.0gsm.

24. The facial masking article of claim 22, wherein the inner layer and the intermediate layer are a laminate of spunbond and meltblown substrates.

25. The facial masking article of any one of claims 1 to 13, wherein the outer protective layer comprises an antimicrobial silver preservative coating having a silver content of 0.2 to 1.0 wt% per gram of outer protective layer.

26. A disposable medical article comprising:

at least one substrate layer; and

a protective layer having a substrate and metal particles in the substrate, the metal particles having a size in at least one dimension in a range of 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth.

27. The disposable medical article according to claim 26, wherein the metal particles comprise at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof.

28. The disposable medical article according to any one of claims 26 to 27, wherein the metal particles comprise silver or copper.

29. The disposable medical article according to any one of claims 26 to 28, wherein the protective layer is paper, a woven material, a nonwoven material, or a laminate thereof.

30. The disposable medical article according to any one of claims 26 to 29, wherein the protective layer is antimicrobial.

31. The disposable medical article according to any one of claims 26 to 30, wherein the protective layer is antiviral.

32. The disposable medical article of any one of claims 26 to 30 being one of a) medical table paper, B) gown, C) curtain, D) dental bib, E) medical garment, F) bed ware.

33. A disposable medical article according to claim 32, wherein the bedding article is one or more of a fitted sheet, or a mattress cover.

34. A wound dressing article comprising:

at least one substrate layer; and

35. The wound dressing article of claim 34, wherein the metal particles comprise at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof.

36. The wound dressing article of any one of claims 34 to 35, wherein the metal particles comprise silver or copper.

37. The wound dressing article of any one of claims 34 to 36, wherein the protective layer is paper, a woven material, a nonwoven material, or a laminate thereof.

38. The wound dressing article of any one of claims 34 to 37, wherein the protective layer is antimicrobial.

39. The wound dressing article of any one of claims 34 to 38, wherein the protective layer is antiviral.

40. The wound dressing article of any one of claims 34 to 39, wherein one or both of the substrate layer and the protective layer are absorbent.

41. A packaging article comprising:

42. The packaging article of claim 41, wherein the metal particles comprise at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof.

43. The packaging article according to any one of claims 41 to 42, wherein the metal particles comprise silver or copper.

44. The packaging article according to any one of claims 41 to 43, wherein the protective layer is paper, a woven material, a nonwoven material, or a laminate thereof.

45. The packaging article according to any one of claims 41 to 44, wherein the protective layer is antimicrobial.

46. An article of packaging according to any one of claims 41 to 46, wherein the protective layer is antiviral.

47. The packaging article of any one of claims 41 to 47, which is a mail envelope, bag, envelope, or carton.

48. An adhesive article comprising:

a protective layer having a substrate and metal particles in the substrate, the metal particles having a size in at least one dimension in a range of 1 to about 200 nanometers, wherein the metal particles are configured to inhibit or prevent pathogen growth;

the adhesive is arranged along one side of the protective layer; and

an optional obscuring layer directly adjacent to and facing the adhesive, the optional obscuring layer configured to be removed to expose the adhesive for placement on a surface.

49. A method of making a protective layer, comprising:

applying a corona discharge treatment to a substrate having a blend of cellulosic fibers and thermoplastic fibers;

applying an aqueous solution to the substrate, the aqueous solution having a metal precursor and a reducing agent; and

applying thermal energy to the aqueous solution, thereby generating metal particles on a surface of the substrate, wherein the metal particles are configured to inhibit or prevent pathogen growth.

50. A method of making a protective layer comprising:

applying an aqueous solution having a metal precursor and a reducing agent to a substrate having a blend of cellulosic fibers and thermoplastic fibers; and

applying an ultraviolet treatment to the aqueous solution and the substrate, thereby producing metal particles on a surface of the substrate, wherein the metal particles are configured to inhibit or prevent pathogen growth.

51. The method of any one of claims 49 through 50, wherein the substrate has a basis weight of about 16.0gsm to about 45.0gsm, wherein the step of applying thermal energy produces 0.05gsm to about 1.5gsm of metal particles supported on the substrate, wherein the metal particles range in size in at least one dimension from 1 to about 200 nanometers with an antiviral log reduction of at least 2.0, an average filtration efficiency of at least 99.71%, and a bacterial filtration efficiency of at least 99.37%.

52. The method of any one of claims 49 to 51, further comprising bonding the protective layer with a middle layer having a basis weight of about 20.0gsm to about 80.0gsm, and an inner layer having a basis weight of about 20.0gsm to about 80.0gsm, wherein the protective layer is a nonwoven material comprising short cellulose fibers and short thermoplastic fibers, and the inner layer and the middle layer are nonwoven substrates comprising thermoplastic fibers.

53. The method of any one of claims 49 to 50, wherein applying thermal energy produces 0.05gsm to about 1.5gsm of metal particles on the surface of the substrate.

54. The method of any one of claims 49 to 50, wherein applying thermal energy generates up to about 1.5gsm of metal particles on the surface of the substrate.

55. The method of any one of claims 49 to 50, wherein applying thermal energy produces 0.05gsm to about 1.5gsm of silver particles.

56. The method of any one of claims 49 to 55, wherein the step of applying thermal energy further comprises applying an ultraviolet treatment to the substrate.

57. The method of any one of claims 49-56, wherein the metal particles comprise at least one of silver, gold, platinum, palladium, aluminum, iron, zinc, copper, cobalt, nickel, manganese, molybdenum, cadmium, iridium, and mixtures thereof.

58. The method of any one of claims 49-57, wherein applying the aqueous solution to the substrate comprises coating the aqueous solution onto the substrate.

59. The method of any one of claims 49 through 58, wherein applying the aqueous solution to the substrate comprises applying an antimicrobial silver anti-corrosive coating having a silver content of 0.2 to 1.0 wt% per gram of protective layer substrate.

60. The method of claim 50, wherein the surface of the substrate is a top surface and the substrate comprises a bottom surface opposite the top surface, wherein the aqueous solution does not permeate through the top surface to the bottom surface.